The Rare Book Collection is comprised of approximately 2,000 rare, fragile, oversized, and special items ranging from political speeches and periodicals, to historical scientific works and literature. Approximately half of the Rare Book Collection comes from the personal library of Alexander S. Salley (1871-1961), South Carolina's first archivist.

The Rare Books collection was formed following the opening of the South Carolina State Library building in 1970. The South Carolina State Library recognizes the need to preserve the rare and fragile materials in our collections, and have housed the Rare Book Collection in archival storage cabinets for protection against environmental factors. Additionally, UV filtering lights have been installed in the area, and measures have been taken to house the most fragile items in archival phase boxes and folders.